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WO2003001290A1 - Synthese de polymeres organiques electrochromes et dispositifs utilisant ces polymeres organiques electrochromes - Google Patents

Synthese de polymeres organiques electrochromes et dispositifs utilisant ces polymeres organiques electrochromes Download PDF

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Publication number
WO2003001290A1
WO2003001290A1 PCT/US2002/020218 US0220218W WO03001290A1 WO 2003001290 A1 WO2003001290 A1 WO 2003001290A1 US 0220218 W US0220218 W US 0220218W WO 03001290 A1 WO03001290 A1 WO 03001290A1
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layer
polymer
electrode
transparent
counter
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PCT/US2002/020218
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WO2003001290A8 (fr
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Chunye Xu
Minoru Taya
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University Of Washington
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Priority to EP02756307A priority Critical patent/EP1412812A4/fr
Priority to CA002451615A priority patent/CA2451615A1/fr
Priority to JP2003507626A priority patent/JP2004531770A/ja
Publication of WO2003001290A1 publication Critical patent/WO2003001290A1/fr
Publication of WO2003001290A8 publication Critical patent/WO2003001290A8/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • G02F1/15165—Polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F2001/1502—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect complementary cell
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof

Definitions

  • the present invention generally relates to electrochromic (EC) materials that exhibit different colors as a function of an applied voltage, and more specifically, to apparatus utilizing specific organic polymer based EC materials, and methods of producing the specific organic polymer based EC materials.
  • EC electrochromic
  • Electrochromic (EC) materials are a subset of the family of chromogenic materials, which includes photochromic materials, and thermochromic materials. These are materials that change their tinting level or opacity when exposed to light (photochromic), heat (t/zermochromic) or electricity (e/ectrochromic). Chromogenic materials have attracted widespread interest in applications relating to the transmission of light.
  • chromogenic materials An early application for chromogenic materials was in sunglasses or prescription eyeglasses that darken when exposed to the sun. Such photochromic materials were first developed by Corning in the late 1960s. Since that time, it has been recognized that chromogenic materials could potentially be used to produce window glass that can vary the amount of light transmitted, although the use of such materials is clearly not limited to that prospective application. Indeed, EC technology is already employed in the displays of digital watches.
  • EC windows have been suggested for use in controlling the amount of daylight and solar heat gain through the windows of buildings and vehicles.
  • EC window technology can save substantial amounts of energy in buildings, and EC glazings may eventually replace traditional solar control technology such as tints, reflective films, and shading devices (e.g., awnings).
  • EC windows Because of their ability to control lighting levels and solar heat gain, EC windows have the potential of reducing the annual U.S. energy consumption by several quadrillion (10 15 ) BTUs, or quads, which is a substantial decrease relative to current consumption rates.
  • the two outside layers of the assembly are transparent electronic conductors. Within the outside layers is a counter-electrode layer and an EC layer, between which is disposed an ion conductor layer. When a low voltage is applied across the outer conductors, ions moving from the counter-electrode to the EC layer cause the assembly to change color. Reversing the voltage moves ions from the EC layer back to the counter-electrode layer, restoring the device to its previous state.
  • all of the layers are preferably transparent to visible light. Both inorganic and organic ion conductive layers are known.
  • EC materials In order to be useful in a window application, or in a display application, EC materials must exhibit long-term stability, rapid redox switching, and exhibit large changes in opacity with changes of state.
  • the EC layer is typically tungsten oxide (WO 3 ).
  • U.S. Patents Nos. 5,598,293, 6,005,705, and 6,136,161 each describe an inorganic thin film EC device based on a tungsten oxide EC layer.
  • Other inorganic EC materials such as molybdenum oxide, are also known. While many inorganic materials have been used as EC materials, difficulties in processing and slow response time associated with many inorganic EC materials have created the need for different types of EC materials.
  • Conjugated, redox-active polymers represent one different type of EC material. These polymers (cathodic or anodic polymers) are inherently electrochromic and can be switched electrochemically or chemically between different color states.
  • a family of redox-active copolymers are described in U.S Patent No. 5,883,220.
  • Another family of nitrogen based hetrocyclic organic EC materials is described in U.S Patent No. 6,197,923. Research into still other types of organic film EC materials continues, in hopes of identifying or developing EC materials that will be useful in EC windows.
  • EC windows While EC windows, or smart windows as they are sometimes called, are expected to represent a significant commercial application of EC technology, one additional potential use of an EC is in producing displays, sometimes referred to smart displays, or digital windows (DWs).
  • DWs digital windows
  • One promising application for DW systems relates to deoxyribonucleic acid (DNA) chip reading.
  • DNA deoxyribonucleic acid
  • oligonucleotide chips have become increasingly important, as more genomes of organisms are sequenced.
  • a suitable system for such an application should employ a switchable window that is readily changed from transparent to nontransparent (e.g., to dark blue) by varying an electric potential polarity (anodic EC polymer sides have a negative polarity and a positive polarity, respectively).
  • These switchable window laminate materials should be convertible to a digital (pixel) array having a size typically ranging from about submicron to about 50 microns, and each array unit should be independently controlled to change from a transparent to a nontransparent state.
  • SPR surface plasmon resonance
  • EC devices that can controllably transition between more than two color states offer the potential of flat panel multicolor displays, using the digital pixel array noted above.
  • a first aspect of the present invention is directed to a method for synthesizing EC polymers and counter-electrodes having properties that can be beneficially employed in EC polymer devices.
  • a second aspect of the present invention is directed to specific configurations of EC polymer based devices, while a third aspect is directed to specific applications of EC polymer devices.
  • synthesizing EC polymers and counter-electrodes two embodiments of the method for synthesizing EC polymers is disclosed, as well as two embodiments for fabricating counter-electrodes for use in EC devices.
  • the first synthesis method is directed toward the production of poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][l,4]dioxepine], also known as PProDOT-Me 2 .
  • PProDOT-Me 2 poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][l,4]dioxepine], also known as PProDOT-Me 2 .
  • equivalent molar amounts of 3,4-dimethoxythiophene and 2,2-dimethyl-l,3-propanediol are dissolved in toluene and heated in the presence of p-toluenesulfonic acid monohydrate (at a concentration of 1.5 mol % of 3,4-dimethoxythiophone) and left for 10-20 hours at a temperature of 110° C.
  • the specified temperature is the boiling point of toluene.
  • the toluene is heated to boiling, toluene vapors are collected and condensed, and then returned to the original solution (i.e. the solution of 3,4-dimethoxythiophene, 2,2-dimethyl-l,3-propanediol, toluene and p-toluenesulfonic acid monohydrate).
  • This process is referred to in the chemical arts as refluxing.
  • a methanol byproduct is produced during the synthesis, and that methanol byproduct significantly reduces the rate of the reaction.
  • the synthesis includes the step of removing the methanol byproduct by absorbing it with calcium chloride. This can be achieved by treating the condensed toluene vapors with calcium chloride before returning the condensed toluene vapors to the original boiling solution. This will remove the methanol byproduct from the condensed toluene vapors. As those of ordinary skill in the art will recognize, such a "salting out" process is sometimes employed in organic synthesis to remove undesirable reactants.
  • a second organic polymer expected to be useful in EC devices is poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole, also known as PBEDOT-NMeCz.
  • This synthesis is somewhat more involved, requiring the formation of two intermediate compounds from readily available reagents. The intermediate compounds are then reacted in the presence of catalyst to obtain the desired product.
  • poly(3,4-ethylenedioxythiophene) (EDOT) is treated with n-butyl lithium in a solution of tetrahydrofuran (THF) at -78° C for one hour.
  • the resulting intermediate compound a Grignard reagent
  • MTF dimethyl foramide
  • That intermediate compound is methylated (preferably using methyl iodine, Mel or CH 3 I), and the temperature is raised to 50° C over a two hour period, yielding a methylated dibromocarbazole (C ⁇ 2 H 6 Br 2 NCH 3 ) intermediate product.
  • This intermediate product is preferably purified by washing with water and ether and dried over sodium sulfate.
  • the two intermediate products are combined in the presence of a nickel catalyst, resulting in the EDOT rings being affixed to the derivatized dibromocarbazole.
  • the reaction is facilitated by maintaining the mixture of the two intermediate products at 50° C over a twelve hour period, to yield BEDOT-NMeCz.
  • a first embodiment of a counter-electrode useful for EC devices can be produced by placing a thin layer of gold on a glass substrate.
  • the thickness of the substrate is on the order of 0.7 mm, with the gold layer being no thicker, and preferably, substantially thinner.
  • a layer of titanium-tungsten (TiW) may be added to the glass substrate first to enliance the gold bond to the substrate.
  • TiW titanium-tungsten
  • less than 25 percent of the substrate surface is covered with the gold layer, which is deposited in a pattern that enhances conductivity across most of the surface area of the counter-electrode.
  • the pattern includes continuous lines, such as may be achieved in a grid pattern.
  • a second embodiment of a counter-electrode useful for EC devices can be produced by replacing the thin layer of gold with a thin layer of highly conductive carbon, such as graphite.
  • the TiW layer is then not required. It is preferred to include an indium tin oxide layer between the glass and the graphite.
  • one embodiment includes both a cathodic EC polymer layer and an anodic EC polymer layer.
  • a different embodiment utilizes a cathodic EC polymer layer and a counter-electrode layer.
  • the embodiment utilizing two EC polymer layers includes transparent electrodes as both top and bottom layers. Indium tin oxide coated glass comprises a preferred transparent electrode. Under the top transparent electrode is disposed the cathodic EC polymer layer.
  • a preferred cathodic polymer is PProDOT-Me 2 . Adjacent to the cathodic polymer layer is - /-
  • a preferred solid electrolyte comprises a gel electrolyte, having a polymer matrix, a solvent carrier, and an ion source. Lithium perchlorate (LiClO 4 ) is a preferred ion source.
  • LiClO 4 Lithium perchlorate
  • One preferred gel electrolyte is polyvinyl chloride (PNC) based and another preferred electrolyte is polymethyl metracrylate (PMMA) based; both contain LiClO .
  • the next layer of the device comprises the anodic polymer layer, preferably comprising PBEDOT- ⁇ MeCz.
  • a final layer comprises the transparent electrode layer noted above.
  • both polymer layers are substantially clear and have a high transmittance.
  • the PBEDOT- ⁇ MeCz never achieves a completely colorless state.
  • each EC polymer layer undergoes a reduction and changes in color from nearly transparent to dark blue.
  • the PProDOT-Me 2 layer attains a darker tint, and is thus more opaque.
  • the color change of the device is very rapid (about 0.5-1 s) and repeatable (more than 10,000 times).
  • the embodiment of the EC device that has only a single EC polymer layer also includes a transparent electrode as a top layer. Again, indium tin oxide coated glass comprises a preferred transparent electrode.
  • transparent electrodes are ITO and doped zinc oxide films deposited on transparent substrates, such as glass or plastics.
  • transparent electrode layer is the cathodic EC polymer layer, preferably PProDOT-Me 2 , followed by a solid electrolyte layer of the type described above. Adjacent to and following the solid electrolyte layer is a counter-electrode layer.
  • a preferred counter-electrode layer includes a conductive coating applied to a transparent substrate (such as glass or plastic). Preferably, the conductive coating does not reduce transmittance through the counter-electrode layer by more than 25 percent.
  • Preferred conductive coatings are gold and graphite, deposited in a pattern that substantially covers the substrate. A preferred pattern includes continuous lines, such as found in a grid.
  • the PProDOT-Me 2 polymer layers In the oxidized state, when no voltage negative (or a positive voltage) is applied, the PProDOT-Me 2 polymer layers is substantially clear, with very little tint. When a negative voltage is applied, the counter-electrode enhances the speed with which the PProDOT-Me 2 polymer layers undergoes a reduction and changes in color from nearly transparent to dark blue. The color change of the device is very rapid (about 0.5 ⁇ 1 s) and repeatable (more than 10,000 times).
  • a first preferred application specific embodiment comprises a smart window that is able to change state from substantially transparent when no voltage (or a positive voltage) is applied, to substantially opaque when a negative voltage is applied.
  • a first embodiment of the smart window is based on a dual polymer EC device, which includes a PProDOT-Me 2 cathodic polymer layer, a solid electrolyte layer, and a PBEDOT-NMeCz anodic polymer layer, as described above.
  • a second embodiment of the smart window is based on a single polymer EC device, utilizing a PProDOT-Me 2 cathodic polymer layer, a solid electrolyte layer, and a counter-electrode layer, also substantially as described above.
  • Still another application specific embodiment is directed to a DW for DNA chip and unknown molecules reading technology based on SPR imaging with high lateral resolution.
  • DNA chip reading/writing technology requires expensive custom photomasks used in the photosynthesizing of oligonucleotides in DNA array fabrication, h this embodiment of the present invention, a DW including a plurality of individually addressable pixels arranged in a grid format is employed in the place of the conventional photomask. A voltage can be applied to each pixel individually, enabling selective masking to be achieved.
  • FIGURE 1 A is a schematic illustration of the synthesis of the monomer
  • ProDOT-Me 2 which when polymerized may be beneficially employed as a cathodic EC polymer
  • FIGURE IB is a schematic illustration of apparatus used in the synthesis of FIGURE 1A;
  • FIGURE 2 schematically illustrates the synthesis of the monomer BEDOT-NMeCz, which may be beneficially employed as an anodic EC polymer once it has been polymerized;
  • FIGURES 3 A and 3B are side elevational schematic illustrations of an EC device that includes a cathodic (PProDOT-Me 2 ) EC polymer film, an anodic (PBEDOT-NMeCz) EC polymer film, and a solid electrolyte layer;
  • FIGURES 4A and 4B are side elevational schematic illustrations of an EC device that includes a cathodic EC polymer film, a solid electrolyte layer and a counter-electrode;
  • FIGURE 5A is a plan view of a gold based counter-electrode being fashioned from a glass wafer;
  • FIGURE 5B is a plan view of a gold based counter-electrode
  • FIGURE 5C is a side elevational view of a gold based counter-electrode
  • FIGURES 6A and 6B illustrate alternative patterns that can be used to form a conductive layer on a counter-electrode
  • FIGURE 7A is a plan view of a graphite based counter-electrode
  • FIGURE 7B is a side elevational view of a graphite based counter-electrode
  • FIGURE 8 A schematically illustrates a working model of a smart window including a PProDOT-Me 2 cathodic polymer film layer and a counter-electrode layer, to which either no voltage or a positive voltage is being applied, thus the smart window is in the oxidized or transparent state;
  • FIGURE 8B schematically illustrates the working model of FIGURE 8A, to which a negative voltage is being applied, thus the smart window is in the reduced or opaque state;
  • FIGURE 9A graphically illustrates the repeatability of a color change in an EC device containing a PProDOT-Me 2 cathodic polymer film and a counter-electrode, in response to changes in applied voltage;
  • FIGURE 9B graphically illustrates the repeatability of color changes in an EC device containing a PProDOT-Me 2 cathodic polymer film and a PBEDOT-NMeCz EC polymer film, in response to changes in applied voltage
  • FIGURE 10A graphically illustrates the transmittance of an EC device containing a PProDOT-Me 2 cathodic polymer film and a gold based counter-electrode in the UN-visible spectrum;
  • FIGURE 10B graphically illustrates the transmittance of an EC device containing a PProDOT-Me 2 cathodic polymer film and a graphite based counter-electrode in the UN- visible spectrum;
  • FIGURE 11 A graphically illustrates the optical switching abilities of an EC device containing a PProDOT-Me 2 cathodic polymer film and a gold based counter-electrode, based on absorbance versus time;
  • FIGURE 11B graphically illustrates the optical switching abilities of an
  • FIGURE 12 graphically illustrates that the time response of an EC device containing a PProDOT-Me cathodic polymer film and a gold based counter-electrode is substantially the same even at different potentials;
  • FIGURE 13 graphically illustrates that the opacity of an EC device containing a PProDOT-Me 2 cathodic polymer film and a gold based counter-electrode is a function of an applied potential
  • FIGURE 14A graphically illustrates the consistent repeatability of a current vs. time relationship for an EC device containing a PProDOT-Me 2 cathodic polymer film and a gold based counter-electrode;
  • FIGURE 14B graphically illustrates the consistent repeatability of a current vs. time relationship for an EC device containing a PProDOT-Me 2 cathodic polymer film and a graphite-based counter-electrode
  • FIGURE 15A graphically illustrates the temperature dependence of an EC device containing a PProDOT-Me 2 cathodic polymer film and a gold based counter-electrode, and an EC device containing a PProDOT-Me 2 cathodic polymer film and a graphite-based counter-electrode, indicating that changes in temperature do not have a significant effect on the current within such devices
  • FIGURE 16 illustrates use of a DW for D ⁇ A chip reading technology based on SPR imaging with high lateral resolution digital window
  • FIGURE 17 is a schematic illustration of the EC devices of the present invention being integrated into a conventional dual pane architectural window
  • FIGURE 18 schematically illustrates the operation of a cathodic polymer EC layer paired to a counter-electrode layer.
  • the present invention is directed to methods for synthesizing EC polymers having properties that can be beneficially employed in an EC polymer device, specific configurations of EC polymer based devices, and specific applications of EC polymer devices.
  • First, the synthesis of the EC polymers will be discussed, followed by a description of specific configurations for an EC device, and finally, specific applications of an EC device will be described. For those not familiar with the workings of EC devices, an overview has been provided at the end of this description. Synthesis of EC Polymers
  • a first organic polymer expected to be useful in EC devices is poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][l,4]dioxepine], also known as dimethyl substituted poly(3,4-propylenedioxythiophene), or PProDOT-Me 2 .
  • FIGURE 1A illustrates the preferred transetherification reaction 10 for the preparation of ProDOT - Me . 3,4-dimethoxythiophene and
  • 2,2-dimethyl-l,3-propanediol are dissolved in toluene and heated in the presence of p-toluenesulfonic acid monohydrate (at a concentration of 1.5 mol% of 3,4-dimethoxythiophene) for 10-20 hours at a temperature of 110° C.
  • This process is referred to in the chemical arts as refluxing, as at a temperature of 110° C toluene boils.
  • a solution is boiled until a fraction of the solution (in this case the toluene fraction, as the 3,4 - dimethoxythiophene, the 2,2-dimethyl-l,3-propanediol and the p-toluenesulfonic acid monohydrate fractions each have higher boiling points) is driven out of the solution as a vapor, and those vapors are then condensed and returned to the original solution.
  • the purpose of employing refluxing in the present invention is because methanol is produced as an undesirable byproduct when 3,4-dimethoxythiophene and 2,2-dimethyl-l,3-propanediol combine to form, the desired product.
  • the presence of the methanol byproduct actually inhibits further reaction between me3,4-dimethoxythiophene and 2,2-dimethyl-l,3-propanediol.
  • the methanol byproduct is preferably removed as it is generated. Refluxing enables the methanol byproduct to be continually removed.
  • Both methanol and toluene have boiling points that are lower than the boiling points of the other fractions; 3,4 - dimethoxythiophene, 2,2-dimethyl-l,3-propanediol, p-toluenesulfonic acid monohydrate and the desired product.
  • By heating the toluene to boiling both the methanol and toluene are removed from the solution.
  • the removed toluene and methanol are condensed and collected in a separate container. Calcium chloride is added to that separate container, which reacts with the methanol to enable the methanol to be removed from the toluene.
  • the condensed toluene then is returned to the original solution (the boiling 3,4 — dimethoxythiophene, 2,2-dimethyl-l,3-propanediol, p-toluenesulfonic acid monohydrate, toluene and the desired product).
  • a preferable step in the synthesis is removing the methanol using calcium chloride.
  • such a "salting out” process is sometimes employed in organic synthesis to remove undesirable reactants.
  • the condensed methanol and condensed toluene are filtered through solid calcium chloride.
  • the resulting monomer, ProDOT - Me 2 is readily polymerized to PProDOT - Me .
  • FIGURE IB schematically illustrates an apparatus 11 used to perform the above synthesis.
  • the reactants (3,4 - dimethoxythiophene,
  • 2,2-dimethyl-l,3-propanediol, and p-toluenesulfonic acid monohydrate are dissolved in toluene in a container 13.
  • Sufficient heat is applied to container 13 (as noted above the boiling point of toluene is 110° C, and while the reagents added to the toluene will somewhat affect the boiling point of the solution, the boiling point of the solution will still be substantially 110° C) so that the solution within the container gently boils.
  • Toluene vapor (and any methanol byproduct) will be driven out of container 13 and into boiling tube 15. The vapors will rise into condenser 17, where the vapors cool and fall into packed calcium chloride 19.
  • the movement of the vapors is indicated by a dashed line, while the movement of the condensed vapors is indicated by solid lines.
  • the methanol is absorbed by the calcium chloride, and the condensed toluene rises to a level 21, where the condensed toluene returns back to container 13 via boiling tube 15.
  • the amount of toluene employed, and the internal volume of apparatus 11 is such that some toluene always remains within container 13 (i.e. the solution never completely boils away) and that the condensed toluene is able to rise through the packed calcium chloride to level 21, such that some condensed toluene returns to container 13.
  • a nitrogen blanket is introduced into apparatus 11, so that ambient oxygen does not introduce undesired byproducts or cross reactions.
  • a second organic polymer expected to be useful in EC devices is poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole, also known as PBEDOT-NMeCz.
  • a preferred synthesis scheme 30 is shown in FIGURE 2. First, (3,4-ethylenedioxythiophene) (EDOT) is treated with n-Butyl lithium in a solution of tetrahydrofuran (THF) at -78° C for one hour. Those of ordinary skill in the art will recognize this step as that employed in the preparation of a Grignard reagent. The resulting Grignard reagent is then treated with magnesium bromide diethyl etherate. The product (i.e., the reagent B), remains in the THF solvent.
  • EDOT (3,4-ethylenedioxythiophene)
  • THF tetra
  • a derivatized dibromocarbazole is combined with lithium hydride in dimethyl foramide (DMF) and kept at less than 10° C for an hour.
  • Methyl groups are slowly added at a 1:1 ratio, and the temperature is raised to 50° C over a two hour period, yielding a methylated derivatized dibromocarbazole product (i.e., the reagent C), which is purified by washing with water and ether, and dried over sodium sulfate.
  • methyl iodine (Mel) is used as a methylating agent.
  • Reagents B and C are combined, resulting in the EDOT rings being affixed to the derivatized dibromocarbazole.
  • EC Device Configurations Another aspect of the present invention is directed at specific configurations of EC devices utilizing EC polymers. Each configuration disclosed herein is based on a laminated system, including at least one EC polymer, a solid or liquid electrolyte, and upper and lower layers of transparent electrodes.
  • a first configuration for an EC device is schematically illustrated in both a transparent state 40a in FIGURE 3 A, and a colored state 40b in FIGURE 3B. Note that structurally, there is no difference in the EC device in either the transparent state or the colored state.
  • the first configuration as collectively illustrated in FIGURES 3A and 3B, thus includes a cathodic (PProDOT-Me 2 ) EC polymer layer and an anodic (PBEDOT-NMeCz) EC polymer layer. It should be noted that the polarity of the applied voltage is important.
  • a top layer is a transparent electrode 42, preferably formed from an indium tin oxide (ITO) coated transparent substrate.
  • the next layer is a cathodic PProDOT-Me 2 ) EC polymer layer, which in.
  • FIGURE 3A is shown as a transparent layer 44a, and in FIGURE 3B is shown as a colored layer 44b.
  • the PProDOT-Me 2 EC polymer layer when no voltage (or a positive voltage) is applied, the PProDOT-Me 2 EC polymer layer is not completely colorless. Instead, a light blue tint can be discerned (hence the shading in transparent layer 44a of FIGURE 3 A). As a negative voltage is applied, the PProDOT-Me 2 EC polymer layer becomes progressively more opaque, until it reaches saturation (a dark blue tint, as indicated by the shading in colored layer 44b of FIGURE 3B).
  • a solid/gel electrolyte layer 46 Following the cathode EC polymer layer is a solid/gel electrolyte layer 46.
  • the solid/gel electrolyte layer is followed by anodic (PBEDOT-NMeCz) EC polymer layer 48, which is also illustrated as being a transparent layer 48a in FIGURE 3 A, and a colored layer 48b in FIGURE 3B. Note that even with no voltage applied (or a positive voltage is applied), PBEDOT-NMeCz is not colorless, and a definite yellowish tint is apparent (hence, the shading in transparent layer 48a of FIGURE 3A).
  • the PBEDOT-NMeCz EC polymer layer becomes progressively more opaque, until it reaches saturation (a moderate blue tint, as indicated by the shading in colored layer 44b of FIGURE 3B).
  • the PBEDOT-NMeCz EC polymer layer is followed by a bottom layer, which is an additional transparent electrode 42, also preferably formed from indium tin oxide (ITO) coated glass.
  • ITO indium tin oxide
  • the first configuration provides a dual EC polymer device, in which the darkness (or opacity) of colored state is increased by using two EC polymers. However, the transmittance of the bleached state is decreased, primarily because the anodic polymer has a noticeable tint in the transparent (or bleached) state.
  • the monomer e.g., BEDOT-NMeCz
  • PBEDOT-NMeCz PBEDOT-NMeCz
  • the cathodic layer which is based on a poly(3,4-propylenedioxythiophene) derivative (PProDOT-Me 2 ), expresses an excellent light transmittance change of 78 percent between the bleached and unbleached states.
  • PProDOT-Me 2 exhibits rapid switching, low oxidation potentials, and excellent stability at ambient and elevated temperature.
  • the electrolyte layer In an EC device, the electrolyte layer must be ionically conductive, but electrically insulating. Both poly(vinyl chloride) (PNC) based and polymethylrnetracrylate (PMMA) based gel electrolytes containing lithium perchlorate (LiClO 4 ) can be employed for solid electrolyte layer 46.
  • solid electrolyte layer 48 is fabricated from PNC (or PMMA), propylene carbonate (PC), ethylene carbonate (EC) and LiClO 4 .
  • the PNC (or PMMA) electrolyte mixture is dissolved in tetrahydrofuran (THF). Either PNC or PMMA based gel electrolytes provide high conductivity (2 mS/cm) at room temperature.
  • the solid polymer matrix of PNC and PMMA provide dimensional stability to the electrolyte, while the high permittivity of the solvents EC and PC enable extensive dissociation of the lithium salts.
  • the low viscosity of EC and PC provides an ionic environment that facilitates high ionic mobility.
  • Another useful gel electrolyte can be prepared from 3% LiClO 4 , 7% PMMA, 20% PC and 70% acetonitrile (AC ⁇ ) (% by weight).
  • a simple synthesis of such a gel is achieved by first dissolving the PMMA and LiClO 4 in AC ⁇ .
  • PC was dried over 4 angstrom molecular sieves and then combined with the other ingredients. The complete mixture was stirred for 10-14 hours at room temperature.
  • a high conductivity (2mS/cm) high viscosity and transparent gel electrolyte was formed.
  • the solid polymer matrix of PMMA provides dimensional stability to the electrolyte, while the high permittivity of the solvents PC and AC ⁇ enable extensive dissociation of the lithium salt.
  • the low viscosity of PC provides an ionic environment that facilitates high ionic mobility.
  • liquid electrolytes are preferred because they facilitate the production of a solid state device (the solvent liquid is contained within the polymer matrix), liquid electrolytes can be used in an EC device.
  • One such liquid electrolyte can be achieved using 0.1M Tetrabutylammonium perchlorate (TBAP) in ACN.
  • TBAP Tetrabutylammonium perchlorate
  • materials other than PVC and PMMA can be employed to provide a polymer matrix for a gel electrolyte, and that materials other than TBAP and LiClO can be employed as ionic sources.
  • a second preferred configuration for an EC device is similarly schematically illustrated in both a transparent state 50a in FIGURE 4 A, and a colored state 50b in FIGURE 4B.
  • the second configuration includes a cathodic PProDOT-Me 2 EC polymer layer and a counter electrode layer, but no anodic PBEDOT-NMeCz EC polymer layer.
  • the polarity of the voltage applied is critical in determining how such devices will respond.
  • the top layer is transparent electrode 42, again, preferably ITO.
  • the next layer is a cathodic PProDOT-Me 2 EC polymer layer, which in FIGURE 4A is shown as a transparent layer 44a, and in FIGURE 4B is shown as a colored layer 44b.
  • a solid/gel electrolyte layer 46 After the cathode EC polymer layer comes a solid/gel electrolyte layer 46.
  • the solid electrolyte layer is followed by a counter-electrode layer 52. No bottom transparent electrode layer is required.
  • Counter-electrode layer 52 is preferably gold based, platinum based, or highly conductive carbon based, and replaces the anodic EC polymer and bottom ITO electrode utilized in the first configuration described above.
  • a preferred highly conductive carbon is graphite. It should be understood that while graphite certainly represents a preferred highly conductive carbon, that other highly conductive carbon materials can also be beneficially employed as a conductive film to be coated onto a transparent substrate to produce a counter-electrode. Many types of conductive carbons are available from a variety of manufacturers, such as Tokai Carbon Co. of Tokyo, Japan; and LORESCO INTERNATIONAL, of Hartiesburg, Mississippi.
  • graphite herein should be considered to be exemplary, rather than limiting the scope of the present invention.
  • nickel can be beneficially employed as a conductive film on a transparent substrate to produce a counter-electrode.
  • the use of a counter-electrode can improve the speed of the color change between states, as well as the high contrast ratio between the two states.
  • the counter-electrode material should be chemically stable, provide high electrical conductivity, and should be easy to fashion into a patterned substrate.
  • Gold, highly conductive carbons, and platinum have been identified as being electrically conductive materials that can be beneficially employed for making a counter-electrode.
  • graphite will be very useful because of its low cost, and gold, while much more expensive, can be used in very thin layers, thereby minimizing the cost of a gold based counter-electrode. Platinum, while electrically conductive, is likely to be so expensive as to preclude its use. It is further contemplated that other conductive materials can be employed to produce the counter-electrode.
  • a gold based counter-electrode was produced as described below, and is illustrated in FIGURES 5A-5C.
  • Polished float glass, 0.7mm thick (available from Delta Technologies, Limited), was used as a substrate.
  • the glass was cut into a 4 inch diameter glass wafer 56. Lithography and sputtering techniques were used for forming a gold pattern 58 on the glass wafer.
  • a layer 60 of titanium-tungsten (TiW) was first sputtered onto the glass substrate.
  • TiW layers have often been used as barrier layers and capping layers in semiconductor manufacturing. The TiW layer helps tightly bind the gold layer to the glass substrate.
  • transmittance through the EC device is very important. If the maximum transmittance through the EC device (or through any part of the device, such as the counter-electrode) is reduced to an unacceptable level, then the device may not be suitable for use in an application such as a window.
  • the checkerboard pattern shown in FIGURES 5A and 5B offers a pattern that, when sufficiently small, is substantially transparent.
  • circular orifices or diamond shaped orifices would be equally useful, as respectively shown in FIGURES 6A and 6B.
  • transmittance is maximized when the total area of the layer of gold (or graphite) is minimized, while conductivity is maximized when the area of the layer of gold (or graphite) is maximized. If an EC device must have excellent transmittance, and a somewhat slower response time is acceptable, then the percentage of the counter-electrode surface area devoted to a gold or graphite layer can be decreased.
  • the percentage of the counter-electrode area devoted to a gold or graphite layer can be increased. It has been empirically determined that covering less than 25 percent of the glass substrate with the conductive material represents a good compromise for EC devices that exhibit both rapid response times and acceptable transparency.
  • highly conductive carbon (such as graphite) based counter-electrodes can also be employed.
  • a first embodiment of a highly conductive carbon based counter-electrode is shown in FIGURES 7A and 7B.
  • a preferred substrate is a polished float glass cuvette plate , about 0.7 mm thick.
  • An ITO coating 64 is applied on one side of the polished float glass cuvette plate, and a carbon coating 62 is then applied over the ITO coating.
  • the highly conductive carbon material is graphite (HITASOL GA.66M).
  • the electrical conductivity of this highly conductive carbon material is known to be not less than 10 "2 S/cm.
  • the glass substrate is covered with the carbon, in order to maintain high transmittance.
  • lithography and sputtering were employed for gold patterning on glass substrate as described above
  • screen printing was employed for forming a graphite pattern on a glass substrate for the highly conductive carbon-based counter-electrode. It is anticipated that because screen printing technology requires less expensive equipment than does lithography and sputtering teclrniques, that mass production of highly conductive carbon-based counter-electrodes may be less expensive than mass production of gold-based counter-electrodes .
  • the glass substrate is coated with indium tin oxide on one side to form a transparent insulating substrate for the counter-electrode.
  • gold can be directly deposited on the glass substrate without ITO glass, but it is preferable to deposit a graphite pattern onto an ITO layer. While less preferred, it should be noted that an acceptable graphite based counter-electrode can be fashioned without the ITO layer illustrated in FIGURE 7B.
  • each polymer layer within these laminated devices are on the order of 150 nanometers in thickness
  • each solid electrolyte layer is approximately 30 microns in thickness
  • the gold patterned layer on the counter-electrode is on the order of 50-100 nanometers in thickness.
  • a preferable range of thickness for a graphite layer in a counter-electrode is also 50-100 nanometers, more preferably 100 nanometers.
  • a preferred thickness for an ITO film is from about 10 nanometers to about 200 nanometers, with more electrical conductivity being provided by a thicker layer.
  • electrical conductivity within an EC device can be manipulated by adjusting a thickness of the ITO layer, especially an ITO layer employed in a counter-electrode.
  • a preferred thickness for a transparent substrate (such as glass or plastic) utilized in a transparent electrode (or counter-electrode) is about 0.5-1.0 millimeters, most preferably 0.7 millimeters.
  • a platinum wire has been successfully employed as a counter-electrode in an EC device generally corresponding to the second configuration as shown in FIGURES 4A and 4B.
  • EC devices having a configuration i.e., a cathodic EC polymer, a solid electrolyte layer, and a non EC polymer counter-electrode
  • PProDOT-Me 2 as the cathodic layer
  • other EC cathodic polymers can be beneficially employed.
  • a single polymer EC device can be fashioned using a counter-electrode and an anodic EC polymer, as opposed to a counter-electrode and a cathodic EC polymer.
  • a single polymer EC device fashioned using a counter-electrode and an anodic EC polymer would be less transparent (i.e. the anodic EC polymer layer would be in its darker state) with no voltage (or a positive voltage) applied, and as a negative voltage is applied to the such as EC device the anodic EC polymer layer would transition to its more transparent state.
  • a sample device based on the single polymer/counter-electrode EC device described above was constructed using rectangular layers substantially 7 mm x 50 mm.
  • An ITO coated 7 mm x 50 mm glass slide was prepared for the transparent electrode, and a layer of PProDOT-Me 2 was deposited on the ITO coated surface.
  • a glass wafer onto which a grid pattern of gold had been deposited was cut into 7 mm x 50 mm plates. Similar 7 mm x 50 mm plates of graphite deposited in a grid pattern were also prepared.
  • a PMMA LiClO gel electrolyte was uniformly placed between the cathodic EC polymer deposited on the ITO slide and the counter-electrode to form layered device.
  • the graphite based counter-electrode differs from the gold based counter-electrode in that a layer of ITO was first placed on the glass substrate before the graphite was deposited, while no such layer was employed in the gold based counter-electrode.
  • a rubber sealant was employed, and the assembled devices were allowed to cure for about 20 hours. It is anticipated that additional curing time might be beneficial, and that 20-30 hours represents a preferred range of cure times.
  • the sealant employed was a parafilm, a readily available, semi-transparent, flexible thermoplastic sealant. A schematic illustration of these working models is provided in FIGURES 8 A and 8B.
  • FIGURE 8A schematically shows a cross-sectional view and a top plan view of a working model in an oxidized state (no voltage or positive voltage applied).
  • the cross-sectional view clearly shows the top layer as being transparent electrode 42, which was prepared by coating glass slide with ITO.
  • transparent layer 44a Immediately adjacent to transparent electrode 42 is transparent layer 44a, a thin film of the cathodic PProDOT-Me 2 EC polymer coated onto the transparent electrode 42.
  • the next layer includes a generally circular solid/gel electrolyte layer 46, which is surrounded by a sealant 53 to prevent any of the electrolyte from leaking.
  • the solid electrolyte layer (and sealant) is followed by counter-electrode layer 52.
  • shape of the solid electrolyte layer defines that area of the EC polymer layer that will change color. Portions of the EC polymer layer that are not in contact with the electrolyte layer will not undergo a change in color.
  • the EC polymer layer coated the entire generally square shaped transparent substrate the sealant was applied as a generally circular mask (i.e. the sealant was applied over the entire surface of the EC polymer layer except for a generally circular portion where no sealant was applied) and the solid electrolyte layer was deposited within the generally circular portion defined by the sealant mask.
  • a quite sharp demarcation between portions of the EC polymer immediately adjacent to the solid electrolyte layer (such portions transitioning from a light state to a dark state under an applied negative voltage) was achieved relative to portions of the EC polymer layer immediately adjacent to the sealant (i.e. not immediately adjacent to the solid electrolyte layer, such portions not transitioning from a light state to a dark state under an applied negative voltage).
  • the sealant mask and electrolyte area can be combined in shapes other than the generally circular shape employed here.
  • FIGURE 8B shows the working model after a negative voltage has been applied, and the portion of the EC polymer layer in contact with electrolyte has changed color, while the balance of the EC polymer layer (i.e. the portion in contact with the sealant) has not.
  • the polarity of the voltage applied determines how such devices will respond.
  • PProDOT-Me 2 was employed as the cathodic EC polymer, and a platinum wire was employed as the counter-electrode.
  • the studies were executed using an potentiostat/galvanostat electrochemical analyzer, CH 1605 A, from CH Instruments, with silver (Ag/Ag + ) as the reference electrode, an ITO-coated one-glass slide as the working electrode, and a platinum (Pt) wire as the counter-electrode.
  • the electrolyte employed (in this case, a liquid electrolyte) was 0.1N TBAP/ACN.
  • Spectro-electrochemistry was carried out on a Narian Corp. UN-Nis- ⁇ IR spectrophotometer.
  • FIGURES 8 and 9 graphically illustrate the fast and repeatable actuation of each of the EC devices described above.
  • FIGURE 9A provides switching data for an EC device with a PProDOT-Me 2 cathodic layer, an electrolyte layer, and a counter-electrode layer
  • FIGURE 9B provides switching data for an EC device with a PProDOT-Me 2 cathodic layer, an electrolyte layer, and a PBEDOT- ⁇ MeCz anodic layer.
  • FIGURE 10B was somewhat darker than gold based counter-electrode device, but the bleached state of the graphite based counter-electrode device was also darker, due to the lower percentage transmittance through the graphite based counter-electrode layer.
  • FIGURE 11A graphically illustrates the results for the gold based counter-electrode device
  • FIGURE 11B graphically illustrates the results for the graphite-based counter-electrode device, based on absorbance under a wavelength of 580nm and an application of 2.0N.
  • Each device exhibited good repeatability and a rapid change in absorbance.
  • the percentage transmittance in the bleached state of the graphite based counter-electrode device was lower than gold based counter-electrode device, but the absorbance response to potential is more rapid in graphite based counter-electrode device.
  • FIGURE 14A graphically illustrates the repeatability of performance during the oxidization and reduction reactions of gold based counter-electrode device
  • FIGURE 14B shows the same result for the graphite-based counter-electrode device, upon varying polarity of a constant potential (i.e., 2.0 volts).
  • a constant potential i.e. 2.0 volts.
  • Each device exhibited very stable repeatability within 1 second, a rapid response time.
  • the magnitude of the current of the graphite-based counter-electrode device was twice that of the gold based counter-electrode. This result is due to the high electric conductivity of the graphite-based counter-electrode, resulting in a color change response time that is shorter than that of the gold based counter-electrode device.
  • FIGURE 1 IB where the absorbance vs. time curve of the graphite-based counter-electrode device has a very steep slope.
  • Temperature dependence of the color change performance of EC materials is also an important factor in designing EC devices.
  • the magnitude of electric current of EC devices under the application of constant voltage represents color change property of the devices.
  • the devices gold and graphite based counter-electrodes
  • Current time curves were measured by a potentiostat/galvanostat electrochemical analyzer at a constant 2.0 volts under various temperatures in the chamber.
  • FIGURE 15 graphically illustrates a plot of the maximum electric current in each EC device as a function of temperature.
  • the graphite-based counter-electrode device using ITO in the counter-electrode can achieve a 0.3-0.8 second response time, upon an applied 2 volts potential, and is repeatable (10,000 times). That performance is faster than achieved in the gold based counter-electrode device (which did not use ITO in the counter-electrode).
  • the gold based counter-electrode device achieved a higher percentage change in transmittance between the transparent and opaque states.
  • the power consumption of the devices are modest, 2-2.5 volts times 10-20 mA.
  • the temperature range under which the switching is stable is a relatively wide, -40°C ⁇ 100°C. In addition, the weight of the devices are minimal.
  • the gold based counter-electrode device and the graphite-based counter-electrode device exhibit good perceived contrast, require a low switching voltage, and hence, are of special interest for use in dialed-tint windows, large areas display, antiglare car rear-view mirrors, and other applications where controllable color switching is useful.
  • an EC device including a PBEDOT-NMeCz anodic layer is employed as a display. Because PBEDOT-NMeCz has a yellowish tint in the oxidized state, and a blue tint in the reduced state, a multicolor display can be achieved.
  • Such an EC device preferably includes a plurality of pixels, each pixel being defined by an individually addressable grid of a dual polymer EC device including a PBEDOT-NMeCz anodic layer. A voltage can be applied to each pixel individually, enabling a flat panel display to be achieved in which the color of each pixel is separately controlled.
  • Still another application specific embodiment is directed to a DW for DNA chip reading technology based on SPR imaging with high lateral resolution.
  • SPR imaging is an accepted technology, which currently utilizes expensive custom photomasks.
  • a DW including a plurality of individually addressable pixels arranged in a grid format is employed in the place of the conventional photomask.
  • the DW includes a plurality of individual pixels, each of which is a laminated EC such as the dual polymer and single polymer devices described above.
  • a voltage can be applied to each pixel individually, enabling selective masking to be achieved, pixel by pixel.
  • a DW provides a switchable window, from transparent to non-transparent (dark blue) by varying electric potential polarity.
  • the laminated EC devices described above are fabricated in a digital (pixel) array, whose size are typically 0.5 - 50 microns across.
  • a DW/SPR imaging system 100 includes a conventional SPR imaging system in which DW 102 is inserted.
  • Conventional elements of DW/SPR imaging system 100 include a flow cell 104, a patterned analytic layer 106, a gold or silver layer 108, a laser light source 110 for directing light to the analytic layer along a first path 112, a first optical element 114 disposed in first light path 112 (for polarizing the light from light source 110), a prism 116 disposed in first light path 112 and adjacent to the analytic layer, such that light traveling along first light path 112 passes through the prism.
  • a second optical element 118 is disposed along a second light path 120, and a charge coupled device (CCD) detector 122 disposed in second light path 120 to receive light focused by second optical element 118.
  • CCD charge coupled device
  • a new SPR system with high spatial resolution is achieved.
  • the high resolution DW/SPR system is expected to analyze unknown molecules and DNAs on a real-time basis at a faster speed rate than can be achieved by conventional SPR imaging systems, by scanning through one group of molecules to another by opening the corresponding several pixels in digital window.
  • the DW can be left in place, and reconfigured by activating different pixels, hi contrast, a photomask would have to be removed and replaced with a different mask to achieve a different masking pattern.
  • FIGURE 17 illustrates single or dual polymer EC devices such as those described above being incorporated into a conventional dual pane window 130. Note that FIGURE 17 includes a front view, a side view, and an expanded portion view, each of which is appropriately labeled.
  • Smart windows differ from conventional windows in that the EC device layered between conventional glass outer pane 134 and inner pane 136, enables wires (not separately shown) extending from the smart window to be coupled to a controllable voltage source, such that the smart window will transition from being generally transparent to being significantly less transparent. If a void or gap 140 separates the panes of conventional glass, preferably the EC device is coupled to outer pane 134, rather than inner pane 136.
  • a first embodiment of a smart window is based on a dual polymer EC device using a ProDOT-Me 2 cathodic polymer layer, a solid electrolyte layer, and a PBEDOT-NMeCz anodic polymer layer, as described above.
  • a second embodiment of a smart window is based on a single polymer EC device, using a PProDOT-Me 2 cathodic polymer layer, a solid electrolyte layer, and a counter-electrode layer, substantially as described above.
  • PProDOT-Me 2 can be used as a cathodically coloring polymer.
  • PProDOT-Me 2 is dark blue color in its fully reduced form, and a very transmissive light blue in its fully oxidized form.
  • This cathodically coloring polymer changes from a light color to a highly colored state upon charge neutralization (i.e. reduction) of the p-doped form.
  • the 7T-7T* transition is depleted at the expense of transitions outside the visible region. Therefore, the dominant wavelength of the color is the same throughout the doping process.
  • FIGURE 17 The EC process of an EC device utilizing a PProDOT-Me 2 cathodic layer, a gel electrolyte containing lithium perchlorate (LiClO ), and a gold based counter-electrode is illustrated in FIGURE 17, where the gold layer plays the role of the second layer required in the paired layer process explained below.
  • the EC process requires paired layers, with the PProDOT-Me 2 layer acting as a first one of the paired layers, and the gold based counter-electrode acting as a second one of the paired layers.
  • a negative voltage has been applied and the PProDOT-Me 2 polymer is in its reduced, highly blue colored state.
  • the gold based counter-electrode layer is attracting the negatively charged perchlorate (ClO 4 ) ions.
  • no voltage (or a positive voltage) is being applied, and the PProDOT-Me 2 polymer is in its oxidized, p-doped light color state.
  • the gold based counter-electrode layer is attracting positively charged lithium (Li) ions.
  • the gel electrolyte separating the PProDOT-Me 2 polymer layer and the gold based counter-electrode layer is ionically conductive but electronically insulating, so the lithium and perchlorate ions are mobile and free to move between the PProDOT-Me 2 polymer side and the gold based counter-electrode side under polarity change of applied potential.

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Abstract

Dans la présente invention, un dispositif polymère électrochrome (EC) lamellé à rapport de contraste élevé et à commutation rapide comprend une électrode transparente, un polymère EC cathodique, un électrolyte gel et une contre-électrode. De préférence le polymère EC cathodique est un dérivé poly(3,4 propylènedioxythiophène), PProDOT Me2. La contre-électrode est un revêtement conducteur déposé sur un substrat transparent, les revêtements préférés comprenant l'or et le carbone fortement conducteur. On peut utiliser la lithographie et la pulvérisation pour façonner/graver une couche d'or et on peut utiliser la sérigraphie pour façonner/graver le graphite. Des études empiriques d'un dispositif préféré indiquent qu'on obtient rapidement (0,5-1s) un rapport de contraste élevé de la transmittance (> 50 %T) à une tension appliquée de 2,5V, qu'on peut répéter au moins 10 000 fois selon les estimations obtenues par électrochimie. Des dispositifs EC à deux couches comprenant PProDOT Me2 sont également présentés, ainsi que des procédés de synthèse des polymères EC préférés. Le procédé de synthèse préféré pour obtenir PProDOT Me2 implique d'effectuer l'ébullition au reflux de réactifs dans du toluène en présence d'un catalyseur, tout en éliminant sans discontinuer le sous-produit méthanol de la solution d'ébullition au reflux.
PCT/US2002/020218 2001-06-25 2002-06-25 Synthese de polymeres organiques electrochromes et dispositifs utilisant ces polymeres organiques electrochromes WO2003001290A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE10328377A1 (de) * 2003-06-24 2005-01-20 Siemens Ag Elektrochromes Anzeigesystem
JP2005255591A (ja) * 2004-03-10 2005-09-22 Kyoto Univ 長鎖アルキル基を有するターチオフェン−フラーレン連結化合物及びその重合体
JP2007526525A (ja) * 2004-03-01 2007-09-13 ユニヴァーシティ オブ ワシントン エレクトロクロミックポリマーをベースにした切替え可能な窓
WO2008028166A1 (fr) * 2006-09-01 2008-03-06 Carnegie Mellon University Polymerisation par metathese grignard universelle
US7874666B2 (en) 2007-03-26 2011-01-25 University Of Washington Through Its Center For Commercialization Smart sunglasses, helmet faceshields and goggles based on electrochromic polymers
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US8154787B2 (en) 2002-06-25 2012-04-10 University Of Washington Electrochromic materials
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US9442339B2 (en) 2010-12-08 2016-09-13 View, Inc. Spacers and connectors for insulated glass units
US9958750B2 (en) 2010-11-08 2018-05-01 View, Inc. Electrochromic window fabrication methods
CN109029768A (zh) * 2018-07-27 2018-12-18 Oppo广东移动通信有限公司 电子设备的温度提醒方法、装置、存储介质和电子设备
US10301871B2 (en) 2012-03-13 2019-05-28 View, Inc. Multi-zone EC windows
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US11067869B2 (en) 2009-12-22 2021-07-20 View, Inc. Self-contained EC IGU
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US20220204398A1 (en) * 2009-03-31 2022-06-30 View, Inc. Counter electrode for electrochromic devices
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040044930A (ko) * 2001-09-18 2004-05-31 코닌클리케 필립스 일렉트로닉스 엔.브이. 전기영동 능동 매트릭스 디스플레이 디바이스
WO2004080712A1 (fr) * 2003-03-07 2004-09-23 Döppner Bauelemente GmbH & Co. KG Element transparent, notamment element en verre de securite
DE10347569A1 (de) * 2003-10-14 2005-06-02 Degussa Ag Keramische, flexible Membran mit verbesserter Haftung der Keramik auf dem Trägervlies
US7333257B2 (en) * 2003-11-19 2008-02-19 University Of Florida Research Foundation, Inc. Device for contacting patterned electrodes on porous substrates
US8988757B2 (en) * 2004-03-12 2015-03-24 The Boeing Company Low vapor pressure solvent for electrochromic devices
US7450294B2 (en) * 2004-03-12 2008-11-11 Boeing Co Multi-color electrochromic apparatus and methods
US8064120B2 (en) * 2004-03-12 2011-11-22 The Boeing Company Aircraft cabin services system including zone controllers for lighting control modules and dimmable windows
US7342708B2 (en) * 2004-04-26 2008-03-11 Tropics Enterprise Co. Ltd. Electrochromic device using poly(3,4-ethylenedioxythiophene) and derivatives thereof
JP4644439B2 (ja) * 2004-05-14 2011-03-02 富士フイルム株式会社 光学濃度変化要素制御装置、及び該制御装置を有する撮影システム
JP4244941B2 (ja) * 2005-02-25 2009-03-25 セイコーエプソン株式会社 発光素子、発光装置および電子機器
US7867616B2 (en) * 2005-06-17 2011-01-11 Honda Motor Co., Ltd. Carbon single-walled nanotubes as electrodes for electrochromic glasses
US20070065954A1 (en) * 2005-09-15 2007-03-22 Minoru Taya Surface plasmon resonance biosensor system for detection of antigens and method for determining the presence of antigens
DE102005052925A1 (de) * 2005-10-14 2007-04-19 Ewald Dörken Ag Baustoffmaterial
US7355161B2 (en) 2005-12-15 2008-04-08 The Boeing Company Systems and methods for controlling windows with variable light transmission
US7970172B1 (en) 2006-01-24 2011-06-28 James Anthony Hendrickson Electrically controlled optical shield for eye protection against bright light
JP4941885B2 (ja) * 2006-04-28 2012-05-30 学校法人早稲田大学 エレクトロクロミックディスプレイ
US7505136B2 (en) 2006-05-16 2009-03-17 The Boeing Company Testing and tuning electrically dimmable windows
DE602006006918D1 (de) * 2006-12-01 2009-07-02 Fraunhofer Ges Forschung Hochtransparentes, elektrochromes Beschichtungsmaterial, Verfahren zur Herstellung dafür und Verwendung des Materials
US7893890B2 (en) * 2007-03-05 2011-02-22 The Boeing Company Electrically dimmable combiner optics for head-up display
FR2917849B1 (fr) * 2007-06-25 2009-09-25 Saint Gobain Materiau semi-electroactif renfermant des composes organiques a activite redox positive ou negative, procede et kit de fabrication de ce materiau, dispositif electrocommandable et vitrages utilisant un tel materiau
US8102586B2 (en) 2007-07-23 2012-01-24 Kuwait University Electronic window shading system for houses, transport vehicles and the like
US7884994B2 (en) * 2007-10-16 2011-02-08 Saint Gobain Glass France Electrochromic layers, device and process of producing same
JP5703024B2 (ja) * 2007-10-30 2015-04-15 ユニバーシティ オブ フロリダ リサーチ ファンデーション インコーポレーティッド 緑色〜透過性可溶性エレクトロクロミックポリマー
US7951902B2 (en) * 2008-01-21 2011-05-31 The University Of Connecticut Conjugated polymers from substituted 3,4-propylenedioxythiophene, compositions, method of making, and use thereof
TWI420261B (zh) * 2008-05-23 2013-12-21 Hon Hai Prec Ind Co Ltd 模仁製造方法
US9782949B2 (en) 2008-05-30 2017-10-10 Corning Incorporated Glass laminated articles and layered articles
US10852613B2 (en) 2009-03-31 2020-12-01 View, Inc. Counter electrode material for electrochromic devices
US8582193B2 (en) 2010-04-30 2013-11-12 View, Inc. Electrochromic devices
US9261751B2 (en) 2010-04-30 2016-02-16 View, Inc. Electrochromic devices
US11187954B2 (en) 2009-03-31 2021-11-30 View, Inc. Electrochromic cathode materials
US10261381B2 (en) 2009-03-31 2019-04-16 View, Inc. Fabrication of low defectivity electrochromic devices
US9664974B2 (en) 2009-03-31 2017-05-30 View, Inc. Fabrication of low defectivity electrochromic devices
US12043890B2 (en) 2009-03-31 2024-07-23 View, Inc. Electrochromic devices
US10156762B2 (en) 2009-03-31 2018-12-18 View, Inc. Counter electrode for electrochromic devices
JP2011068537A (ja) * 2009-09-28 2011-04-07 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス
US8404515B2 (en) 2010-03-25 2013-03-26 The University Of Connecticut Formation of conjugated polymers for solid-state devices
US9759975B2 (en) 2010-04-30 2017-09-12 View, Inc. Electrochromic devices
KR101121165B1 (ko) * 2010-05-26 2012-03-20 광주과학기술원 Ｐ?도핑된 공액 고분자 전해질 및 이를 이용한 유기전자소자
US8586702B2 (en) 2010-08-27 2013-11-19 University Of Delaware Substituted 3,4-propylenedioxythiophene monomers and 3,4-propylenedioxythiophene-based crosslinkers and polymers thereof
US8380393B1 (en) 2010-09-03 2013-02-19 The Boeing Company Variably dimmable window system and method
WO2012118818A2 (fr) 2011-03-02 2012-09-07 University Of Connecticut Monomères à base de sélénium et polymère conjugués, procédés de fabrication et d'utilisation associés
WO2014018472A1 (fr) 2012-07-23 2014-01-30 The University Of Connecticut Copolymères électrochromes à partir de précurseurs, leur procédé de fabrication et leur utilisation
BR112015002148A2 (pt) 2012-08-01 2017-07-04 Ppg Ind Ohio Inc sistema de janela inteligente aeroespacial
CN103909868B (zh) * 2013-01-04 2016-04-06 常州雅谱智能变色光学器件有限公司 车辆前视智能防眩光装置及其防眩光镜的制造方法
SG11201601614YA (en) * 2013-09-10 2016-04-28 Univ Nanyang Tech Electrochromic device
CN103524718B (zh) 2013-09-29 2015-09-02 京东方科技集团股份有限公司 一种红色电致变色材料及其制备方法与组件
US9933680B2 (en) 2014-04-28 2018-04-03 University Of Washington Heat-resistant electrolyte materials and electrochromic devices including them
US11891327B2 (en) 2014-05-02 2024-02-06 View, Inc. Fabrication of low defectivity electrochromic devices
US10323178B2 (en) 2014-05-16 2019-06-18 The University Of Connecticut Color tuning of electrochromic devices using an organic dye
WO2015179789A1 (fr) * 2014-05-23 2015-11-26 University Of Florida Research Foundation, Inc. Polymères électrochromes à absorption large
US10345671B2 (en) 2014-09-05 2019-07-09 View, Inc. Counter electrode for electrochromic devices
EP3221167B1 (fr) 2014-11-21 2020-10-28 Gentex Corporation Ensemble électro-optique
EP3224670B1 (fr) 2014-11-26 2023-04-12 View, Inc. Contre-électrode pour dispositifs électrochromiques
KR101777779B1 (ko) 2014-12-23 2017-09-12 광주과학기술원 P-도핑된 공액 저분자 전해질 및 이를 이용한 유기전자소자
EP3310608B1 (fr) 2015-06-16 2022-09-21 Gentex Corporation Système d'affichage tête-haute
CN119916619A (zh) * 2015-07-14 2025-05-02 唯景公司 用于电致变色装置的对电极
CN107924084A (zh) 2015-08-14 2018-04-17 金泰克斯公司 平视显示器系统
JP6958814B2 (ja) 2016-07-22 2021-11-02 積水化学工業株式会社 調光材料、調光フィルム及び調光積層体
WO2018039428A1 (fr) * 2016-08-26 2018-03-01 Board Of Regents, The University Of Texas System Dispositifs électrochromes et leurs procédés de fabrication et d'utilisation
CN107118960B (zh) * 2017-05-15 2019-10-01 京东方科技集团股份有限公司 一种基因测序芯片、基因测序系统及其测序方法
EP3692413B1 (fr) 2017-11-27 2021-09-15 Gentex Corporation Affichages polarisés commutables
US11624861B2 (en) 2017-11-27 2023-04-11 Gentex Corporation Vehicular rearview assemblies having polarized displays using electro-optic element
US10775649B2 (en) 2018-05-17 2020-09-15 Cardinal Cg Company Elastomeric optical device and related methods
US11340479B2 (en) 2018-05-17 2022-05-24 Cardinal Cg Company Elastomeric optical device and related operation methods
CN110320722B (zh) * 2019-07-24 2021-10-26 东南大学 可见光至中红外等离激元异质微腔电致变色器件
US11780594B2 (en) 2019-10-02 2023-10-10 Ppg Industries Ohio, Inc. Transparency including a wireless sensor
US20210232014A1 (en) * 2019-12-22 2021-07-29 Jianguo Mei Electrochromic devices with increased lifetime
CN111171292B (zh) * 2020-02-14 2023-02-03 南京宜凯瑞新材料有限公司 两亲性电致变色聚合物及其制备方法
WO2021231635A1 (fr) * 2020-05-14 2021-11-18 The Board Of Trustees Of The Leland Stanford Junior University Détection optique sans étiquette de potentiels bioélectriques à l'aide de matériaux électrochromes
US12259348B2 (en) * 2020-06-17 2025-03-25 Automat Solutions, Inc. Multichannel matrix-based electrochemical testing system
US20240367489A1 (en) * 2020-09-14 2024-11-07 Scott Freeman Colored automotive windows
JP7716802B2 (ja) * 2022-08-08 2025-08-01 国立研究開発法人物質・材料研究機構 積層体、組成物、及びエレクトロクロミックデバイスの製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4993810A (en) * 1989-04-14 1991-02-19 Ford Motor Company Electrochromic devices comprising metal salts in an ion conductive material
US5042923A (en) * 1988-06-27 1991-08-27 Allied-Signal, Inc. Adjustable tint window with electrochromic conductive polymer
US5724176A (en) * 1993-03-30 1998-03-03 Nippon Oil Co., Ltd. Counterelectrode for smart window and smart window
US5888431A (en) * 1994-07-22 1999-03-30 Gentex Corporation Electrochromic layer and devices comprising same
US6011642A (en) * 1997-04-18 2000-01-04 U.S. Philips Corporation Electrochromic element, a display device provided with same and a method of manufacturing an electrochromic layer

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US174377A (en) * 1876-03-07 Improvement in music-portfolios
JPH0678492B2 (ja) 1986-11-27 1994-10-05 昭和電工株式会社 高電導性重合体組成物及びその製造方法
US4973391A (en) * 1988-08-30 1990-11-27 Osaka Gas Company, Ltd. Composite polymers of polyaniline with metal phthalocyanine and polyaniline with organic sulfonic acid and nafion
US5006633A (en) * 1988-08-31 1991-04-09 Nippon Oil Company, Limited Novel compolymers and electroactive polymers derived therefrom
JP2640548B2 (ja) * 1990-02-20 1997-08-13 日本石油株式会社 エレクトロクロミック材料および表示素子
US5883220A (en) 1992-01-12 1999-03-16 Centre National De La Recherche Scientifique Redox copolymers and their use in preparing mixed conduction materials
DE69332342T2 (de) 1992-04-10 2003-06-05 Sun Active Glass Electrochromics, Inc. Elektrochrome strukturen und verfahren
IT1261163B (it) 1993-01-22 1996-05-09 Siv Soc Italiana Vetro Vetro elettrocromico per auto ed edilizia.
US6136161A (en) 1993-11-12 2000-10-24 Ppg Industries Ohio, Inc. Fabrication of electrochromic device with plastic substrates
DE4413403A1 (de) 1994-04-18 1995-10-19 Inst Neue Mat Gemein Gmbh Elektrochrome Dünnschichtsysteme und deren Komponenten
JP3844016B2 (ja) 1995-10-27 2006-11-08 日産化学工業株式会社 新規重合体及びその製造法と利用法
JPH11142891A (ja) * 1997-11-05 1999-05-28 Nippon Oil Co Ltd エレクトロクロミックミラー
US6359149B1 (en) 1999-02-23 2002-03-19 The United States Of America As Represented By The Secretary Of The Air Force Bithienylnaphthalene- and bis(3,4-ethylenedioxythienyl)naphthalene-based monomers and polymers
US6555945B1 (en) * 1999-02-25 2003-04-29 Alliedsignal Inc. Actuators using double-layer charging of high surface area materials
JP2001209078A (ja) * 2000-01-26 2001-08-03 Nippon Mitsubishi Oil Corp エレクトロクロミック素子
US6373618B1 (en) * 2000-05-04 2002-04-16 Schott-Donnelly, Llc Chromogenic glazing for automobiles and display filters
US6730212B1 (en) * 2000-10-03 2004-05-04 Hrl Laboratories, Llc Sensor for chemical and biological materials
KR20040014444A (ko) * 2000-12-23 2004-02-14 웬 루 이온성 액체를 구비한 긴 수명 공명 폴리머 전기화학 장치
DE60218814T2 (de) * 2001-01-03 2007-12-06 Santa Fe Science and Technology, Inc., Santa Fe Stabile, konjugiertes polymer enthaltende elektrochrome vorrichtungen mit ionischen flüssigkeiten
CN100540627C (zh) * 2001-11-21 2009-09-16 佛罗里达州立大学 电致变色聚合物和聚合物电致变色装置
US6734956B2 (en) * 2002-05-06 2004-05-11 Reichert, Inc. Optical configuration and method for differential refractive index measurements

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5042923A (en) * 1988-06-27 1991-08-27 Allied-Signal, Inc. Adjustable tint window with electrochromic conductive polymer
US4993810A (en) * 1989-04-14 1991-02-19 Ford Motor Company Electrochromic devices comprising metal salts in an ion conductive material
US5724176A (en) * 1993-03-30 1998-03-03 Nippon Oil Co., Ltd. Counterelectrode for smart window and smart window
US5888431A (en) * 1994-07-22 1999-03-30 Gentex Corporation Electrochromic layer and devices comprising same
US6011642A (en) * 1997-04-18 2000-01-04 U.S. Philips Corporation Electrochromic element, a display device provided with same and a method of manufacturing an electrochromic layer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1412812A4 *

Cited By (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8154787B2 (en) 2002-06-25 2012-04-10 University Of Washington Electrochromic materials
DE10328377A1 (de) * 2003-06-24 2005-01-20 Siemens Ag Elektrochromes Anzeigesystem
JP2007526525A (ja) * 2004-03-01 2007-09-13 ユニヴァーシティ オブ ワシントン エレクトロクロミックポリマーをベースにした切替え可能な窓
EP1756658A4 (fr) * 2004-03-01 2009-11-04 Univ Washington Vitrages commutables utilisant des polymeres electrochromes
JP2005255591A (ja) * 2004-03-10 2005-09-22 Kyoto Univ 長鎖アルキル基を有するターチオフェン−フラーレン連結化合物及びその重合体
US8288508B2 (en) 2006-09-01 2012-10-16 Carnegie Mellon University Universal grignard metathesis polymerization
WO2008028166A1 (fr) * 2006-09-01 2008-03-06 Carnegie Mellon University Polymerisation par metathese grignard universelle
US7874666B2 (en) 2007-03-26 2011-01-25 University Of Washington Through Its Center For Commercialization Smart sunglasses, helmet faceshields and goggles based on electrochromic polymers
US8514476B2 (en) 2008-06-25 2013-08-20 View, Inc. Multi-pane dynamic window and method for making same
EP2313591A4 (fr) * 2008-06-25 2012-04-18 Soladigm Inc Fenêtre dynamique à carreaux multiples et procédé de fabrication
US10437126B2 (en) 2008-06-25 2019-10-08 View, Inc. Multi-pane dynamic window and method for making same
CN102203370A (zh) * 2008-06-25 2011-09-28 索拉迪格姆公司 多窗格动态窗户及其制造方法
US8749870B2 (en) 2008-06-25 2014-06-10 View, Inc. Multi-pane dynamic window and method for making same
US9110345B2 (en) 2008-06-25 2015-08-18 View, Inc. Multi-pane dynamic window and method for making same
US9618819B2 (en) 2008-06-25 2017-04-11 View, Inc. Multi-pane dynamic window and method for making same
US20220204398A1 (en) * 2009-03-31 2022-06-30 View, Inc. Counter electrode for electrochromic devices
US12353109B2 (en) 2009-12-22 2025-07-08 View Operating Corporation Electrochromic cathode materials
US11927866B2 (en) 2009-12-22 2024-03-12 View, Inc. Self-contained EC IGU
US11314139B2 (en) 2009-12-22 2022-04-26 View, Inc. Self-contained EC IGU
US11067869B2 (en) 2009-12-22 2021-07-20 View, Inc. Self-contained EC IGU
US9958750B2 (en) 2010-11-08 2018-05-01 View, Inc. Electrochromic window fabrication methods
CN103261960A (zh) * 2010-12-08 2013-08-21 唯景公司 绝缘玻璃装置的改良隔板
CN103261960B (zh) * 2010-12-08 2017-08-08 唯景公司 绝缘玻璃装置的改良隔板
US12025900B2 (en) 2010-12-08 2024-07-02 View, Inc. Spacers and connectors for insulated glass units
US10444589B2 (en) 2010-12-08 2019-10-15 View, Inc. Spacers and connectors for insulated glass units
US10782583B2 (en) 2010-12-08 2020-09-22 View, Inc. Spacers for insulated glass units
US10901286B2 (en) 2010-12-08 2021-01-26 View, Inc. Spacers and connectors for insulated glass units
US9158173B2 (en) 2010-12-08 2015-10-13 View, Inc. Spacers for insulated glass units
US11960189B2 (en) 2010-12-08 2024-04-16 View, Inc. Spacers for insulated glass units
US9910336B2 (en) 2010-12-08 2018-03-06 View, Inc. Spacers and connectors for insulated glass units
US9442339B2 (en) 2010-12-08 2016-09-13 View, Inc. Spacers and connectors for insulated glass units
US11740528B2 (en) 2010-12-08 2023-08-29 View, Inc. Spacers for insulated glass units
US9897888B2 (en) 2010-12-08 2018-02-20 View, Inc. Spacers for insulated glass units
US10914118B2 (en) 2012-03-13 2021-02-09 View, Inc. Multi-zone EC windows
US12393087B2 (en) 2012-03-13 2025-08-19 View Operating Corporation Multi-zone EC windows
US11635666B2 (en) 2012-03-13 2023-04-25 View, Inc Methods of controlling multi-zone tintable windows
US11306532B2 (en) 2012-03-13 2022-04-19 View, Inc. Multi-zone EC windows
US11899330B2 (en) 2012-03-13 2024-02-13 View, Inc. Multi-zone EC windows
US11078721B2 (en) 2012-03-13 2021-08-03 View, Inc. Multi-zone EC windows
US10301871B2 (en) 2012-03-13 2019-05-28 View, Inc. Multi-zone EC windows
US12429742B2 (en) 2012-03-13 2025-09-30 View Operating Corporation Methods of controlling multi-zone tintable windows
US12153320B2 (en) 2012-03-13 2024-11-26 View, Inc. Multi-zone EC windows
US12259627B2 (en) 2012-03-13 2025-03-25 View Operating Corporation Multi-zone EC windows
US12345990B2 (en) 2012-03-13 2025-07-01 View Operating Corporation Multi-zone EC windows
US10975612B2 (en) 2014-12-15 2021-04-13 View, Inc. Seals for electrochromic windows
US11555346B2 (en) 2014-12-15 2023-01-17 View, Inc. Seals for electrochromic windows
CN109029768A (zh) * 2018-07-27 2018-12-18 Oppo广东移动通信有限公司 电子设备的温度提醒方法、装置、存储介质和电子设备

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US7002722B2 (en) 2006-02-21
JP2008197679A (ja) 2008-08-28
US20020196518A1 (en) 2002-12-26
EP1412812A1 (fr) 2004-04-28
CA2451615A1 (fr) 2003-01-03
JP2004531770A (ja) 2004-10-14
EP1412812A4 (fr) 2009-07-22
US20050157369A1 (en) 2005-07-21
WO2003001290A8 (fr) 2003-02-20
US20040143091A1 (en) 2004-07-22
US6747780B2 (en) 2004-06-08

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